WO2016017080A1 - Objet moulé et procédé de production associé - Google Patents
Objet moulé et procédé de production associé Download PDFInfo
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- WO2016017080A1 WO2016017080A1 PCT/JP2015/003471 JP2015003471W WO2016017080A1 WO 2016017080 A1 WO2016017080 A1 WO 2016017080A1 JP 2015003471 W JP2015003471 W JP 2015003471W WO 2016017080 A1 WO2016017080 A1 WO 2016017080A1
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- reinforcing fibers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
- B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
- B29C70/222—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure the structure being shaped to form a three dimensional configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/24—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least three directions forming a three dimensional structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/545—Perforating, cutting or machining during or after moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/12—Thermoplastic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0872—Prepregs
- B29K2105/0881—Prepregs unidirectional
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
Definitions
- the present invention relates to a molded body and a manufacturing method thereof, and more particularly to a fiber reinforced resin molded body using reinforcing fibers and a resin and a manufacturing method thereof.
- thermosetting prepreg sheet thermosetting prepreg sheet
- reinforcing fibers such as glass fiber
- thermosetting resins such as thermosetting epoxy resin
- thermosetting prepreg sheet cannot be remolded, and there is a problem that a low temperature cold storage warehouse is required for storing the uncured (before thermosetting) sheet. Further, it takes a long time to cure the thermosetting resin, and there is a problem in productivity.
- the carbon fiber has anisotropy that the strength in the shear direction is small although it has excellent strength in the fiber axis direction.
- the carbon fibers are aligned in one direction to form a sheet, and a plurality of resin sheets (prepreg sheets) provided with a thermoplastic resin are laminated and arranged so that the fiber axis directions are different, and pressed.
- a technique for manufacturing a molded body has been proposed (Patent Document 1).
- thermoplastic resin As a fiber reinforced molded product using a thermoplastic resin, the thermoplastic resin and the reinforcing fiber are agitated with a screw-type stirrer, etc., so that the axial direction is randomly oriented in the thermoplastic resin.
- a screw-type stirrer etc.
- fibers There are also known fibers.
- the molded body obtained in this way is unlikely to generate anisotropy in which mechanical properties such as strength and elastic modulus differ depending on the direction, but carbon fibers are stirred during the stirring of the thermoplastic resin and the reinforcing fibers. Such a reinforcing fiber may be broken and cut, and the strength of the resulting molded product may be reduced.
- the inventors of the present application have developed a laminate in which fiber reinforced resin materials including a bundle of strip-shaped reinforcing fibers (reinforced fiber bundles) in which a thermoplastic resin and a plurality of reinforcing fibers are arranged in one direction are randomly stacked. It has been found that a molded article having excellent strength can be obtained by heating and pressurizing.
- a flat article such as a plate-like article, or a molded article such as a tray having a depth of about 1 to 2 cm and a shallower depth than the length of a fiber constituting a bundle of strip-like reinforcing fibers. If so, a product without any problems was obtained.
- a hole may be formed in a part of the molded body, and there is room for further improvement in appearance and strength.
- the present invention has been made in view of such problems, and an object thereof is to provide a molded article having excellent appearance quality and excellent strength, and a method for producing the same.
- a molded body according to the present invention uses a fiber reinforced resin material including a thermoplastic resin and a bundle of strip-shaped reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction.
- the bundle of strip-like reinforcing fibers is made of a fiber reinforced resin material including a first layer in which three-dimensionally randomly laminated bundles, a thermoplastic resin, and reinforcing fibers of long fibers, And a second layer formed on at least one side of the layer.
- the second layer may be formed on both surfaces of the first layer.
- the reinforcing fiber used for the second layer 20 may be in a woven shape.
- the length of the bundle of strip-shaped reinforcing fibers is preferably 5 mm or more and 500 mm or less.
- thermoplastic resin used for the first layer and the second layer may be an epoxy resin.
- thermoplastic resin may be a post-reaction type thermoplastic resin.
- the reinforcing fibers used for the first layer and the second layer may be carbon fibers.
- the method for producing a molded body according to the present invention includes a step of producing a sheet-like material made of a fiber reinforced resin material including a thermoplastic resin and a long fiber reinforced fiber, and the thermoplastic resin and the plurality of reinforced fibers.
- the long-fiber reinforcing fibers may be in the form of a woven fabric.
- a molded product (molded product) having excellent strength such as excellent appearance quality and impact resistance can be provided.
- FIG. 1A is a cross-sectional perspective view schematically showing the structure of a molded body according to an embodiment of the present invention.
- FIG. 1B is a cross-sectional perspective view schematically showing the structure of a molded body according to another embodiment of the present invention.
- FIG. 2 is a diagram showing a part of the first layer of the molded body according to the embodiment of the present invention.
- FIG. 3 is a diagram showing a flat molded body in the example.
- FIG. 4 is an external view of a molded body having unevenness in the example when viewed from the surface.
- FIG. 5 is an external view of the molded article having unevenness in the example when viewed from the back side.
- FIG. 6 is an external view of the molded body having unevenness in Reference Example 1 when viewed from the surface.
- FIG. 7 is an external view of the molded body having unevenness in Reference Example 2 when viewed from the surface.
- FIG. 8 is an external view of the molded article having unevenness in Reference Example 2 when
- FIG. 1A is a cross-sectional perspective view schematically showing the structure of a molded body according to an embodiment of the present invention.
- the molded body 1 is a fiber-reinforced resin molded body using reinforcing fibers and a resin, and is a sheet-like prepreg (prepreg sheet). As shown in FIG. 1A, the molded body 1 includes a layered first layer 10 and a sheet-like second layer 20 formed on one surface of the first layer 10.
- the second layer 20 may be formed on both surfaces of the first layer 10 as shown in FIG. 1B. That is, the second layer 20 only needs to be formed on at least one of both surfaces of the first layer 10.
- the first layer 10 uses a fiber reinforced resin material including a thermoplastic resin and a bundle of strip-shaped reinforcing fibers (reinforced fiber bundle) in which a plurality of reinforcing fibers are arranged in one direction. It is a layer of a laminated structure in which a bundle of strip-shaped reinforcing fibers is randomly laminated in three dimensions.
- the fiber reinforced resin material constituting the first layer 10 is thermoplastic because it includes a thermoplastic resin and a bundle of reinforcing fibers. Therefore, even after it is once cured to produce the molded body 1, it can be easily deformed into an arbitrary shape by heating and pressing the molded body 1.
- the thickness of the first layer 10 is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more. When the thickness of the first layer 10 is less than 100 ⁇ m, the obtained molded body 1 may not have sufficient fracture toughness, impact resistance, and bending strength.
- the thickness of the first layer 10 is preferably 300 ⁇ m or more, more preferably 500 ⁇ m or more.
- 20 cm or less Preferably it is 10 cm or less, More preferably, it is 5 cm or less, More preferably, 1 cm or less is good.
- the first layer 10 is obtained by randomly stacking a bundle of strip-like reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction in a three-dimensional manner.
- a bundle of strip-shaped reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction is randomly laminated in three dimensions means that a plurality of reinforcing fibers are arranged in one direction as shown in FIG.
- FIG. 2 is a diagram showing a part of the first layer of the molded body according to the embodiment of the present invention, and shows a state in which a bundle of strip-shaped reinforcing fibers is randomly laminated in three dimensions.
- a molded body having more excellent impact resistance and fracture toughness can be obtained by randomly stacking a bundle of strip-like reinforcing fibers 10a in three dimensions.
- the strip-shaped reinforcing fiber bundle 10a does not necessarily have to be inclined with respect to the surface direction of the first layer 10, and the plurality of strip-shaped reinforcing fiber bundles 10a include the first reinforcing fiber bundle 10a. What is not inclined with respect to the surface direction of the layer 10 may be included.
- the fiber reinforced resin material constituting the first layer 10 may contain substances other than the reinforced fiber and the thermoplastic resin, such as a catalyst, an antioxidant, and a pigment.
- the thermoplastic resin used in the molded body 1 in the present embodiment is an epoxy resin, polyamide resin, acrylic resin, polyphenylene sulfide resin, polyvinyl chloride resin, polyethylene, polypropylene, polyacetal resin, polycarbonate, polyurethane, polybutylene terephthalate, acrylonitrile.
- Thermoplastic resins such as butadiene styrene (ABS) resin, modified polyphenylene ether resin, phenoxy resin, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, aromatic polyester, 6-nylon, or 6,6-nylon In addition, it is thermoplastic even after being cured.
- the fiber-reinforced resin molded body obtained using such a thermoplastic resin can be easily deformed by heating even after molding, and can be easily recycled.
- the post-reaction type thermoplastic resin is a reaction type resin that cures by adding a curing agent such as a crosslinking agent, a catalyst, a polymerization initiator, a polymerization accelerator, etc. Even after curing, it has thermoplasticity.
- a curing agent such as a crosslinking agent, a catalyst, a polymerization initiator, a polymerization accelerator, etc. Even after curing, it has thermoplasticity.
- the post-reaction type thermoplastic epoxy resin in the present embodiment includes a resin that becomes a phenoxy resin after the reaction.
- the post-reaction type thermoplastic resin obtained by reaction after being applied to a bundle of strip-shaped reinforcing fibers is impregnated with the resin even inside the bundle of reinforcing fibers, so that the fracture toughness, bending strength, impact resistance, etc. It is preferable from the viewpoints of strength improvement and stability of various performances such as strength and moldability.
- thermoplastic resins may be used in combination of plural kinds.
- thermosetting resin may be blended with these thermoplastic resins without departing from the object of the present invention.
- the post-reaction type thermoplastic resin is particularly suitable for post-reaction. It is preferable to use a mold type thermoplastic epoxy resin. When carbon fibers are used as the reinforcing fibers, it is preferable to use a post-reaction type thermoplastic epoxy resin from the viewpoint of affinity with the carbon fibers. By producing the molded body 1 using a fiber-reinforced resin material composed of a post-reaction type thermoplastic epoxy resin and carbon fiber, strength, durability and stability are further improved. From the viewpoint of productivity, it is preferable to use 6,6-nylon, which can complete the reaction at about 160 ° C., as the post-reaction type thermoplastic resin.
- thermoplastic resin can be liquid or dissolved or dispersed in a solvent at room temperature before being cured with a curing agent. Because the molecular weight of the thermoplastic resin before the reaction is small compared to the plastic resin and the fluidity is increased, and the polymer can be polymerized after the reaction (for example, the number average molecular weight is 10,000 or more and 30,000 or more). Moreover, since the state of crosslinking can also be adjusted, the thermoplastic resin can be impregnated into the bundle of reinforcing fibers. In addition, this allows the thermoplastic resin to exist even inside the bundle of reinforcing fibers, so that the reinforcing fibers and the thermoplastic resin are sufficiently entangled (contacted), and spaces such as bubbles are formed. Can be suppressed. Therefore, the molded body 1 obtained using the fiber reinforced resin material composed of the thermoplastic resin has excellent strength, and has stable strength with suppressed variation. Moreover, the molded object 1 obtained in this way can also adjust flexibility and heat deformability.
- the glass transition point of the thermoplastic resin is preferably 90 to 200 ° C. From the viewpoint of the thermal stability of the obtained molded body 1, the glass transition point of the thermoplastic resin is more preferably 95 ° C. or higher. On the other hand, from the viewpoint of moldability of the obtained molded body 1, the glass transition point of the thermoplastic resin is more preferably 170 ° C. or lower, and further preferably 150 ° C. or lower.
- the glass transition point can be measured by differential scanning calorimetry (DSC) using a cured thermoplastic resin.
- Examples of the reinforcing fibers used in the molded body 1 in the present embodiment include inorganic fibers, organic fibers, metal fibers, or those obtained by combining these. Specifically, carbon fiber, graphite fiber, silicon carbide fiber, alumina fiber, tungsten carbide fiber, boron fiber, glass fiber, basalt fiber, para-aramid fiber, meta-aramid fiber, ultrahigh molecular weight polyethylene fiber, polyarylate Examples thereof include fibers, PBO (polyparaphenylene benzoxazole) fibers, polyphenylene sulfide (PPS) fibers, polyimide fibers, fluorine fibers, polyvinyl alcohol (PVA fibers), stainless steel, and iron.
- PBO polyparaphenylene benzoxazole
- carbon fibers or basalt fibers are particularly preferable.
- the carbon fiber can be PAN-based or pitch-based, but is not particularly limited. Among these, from the viewpoint of the balance between strength and elastic modulus, it is preferable to use PAN-based carbon fibers as reinforcing fibers.
- a bundle in which a plurality of reinforcing fibers are arranged in one direction and bundled is used.
- a bundle of a plurality of reinforcing fibers arranged in one direction is a combination of the fiber axis directions of the plurality of reinforcing fibers constituting the bundle of reinforcing fibers. Therefore, as long as the approximate axial directions of the reinforcing fibers constituting the reinforcing fiber bundle are matched, the reinforcing fiber bundle and the reinforcing fibers constituting the reinforcing fiber bundle may be bent or meandering.
- the reinforcing fiber and the bundle of reinforcing fibers bend, meander or partially collapse and spread due to the concavo-convex shape of the molded body, the entanglement of the reinforcing fibers and the bundles thereof.
- the concept that a bundle of strip-like reinforcing fibers is randomly stacked in three dimensions is a state in which the reinforcing fibers and the bundle of reinforcing fibers are deformed by bending or meandering due to pressure or the like. are also included.
- the bundle of reinforcing fibers means that two or more reinforcing fibers are bundled, and even if they are bundled with a sizing agent, they are bundled without using a sizing agent. It may be. From the viewpoint of productivity, a product focused with a sizing agent is preferable. In addition, when using a sizing agent, it is good to use a thing with high affinity with said thermoplastic resin. By using a sizing agent that has a high affinity with the thermoplastic resin, it becomes easy to impregnate the thermoplastic fiber into the bundle of reinforcing fibers, so that the fiber-reinforced resin molded article has excellent strength and stable strength. Can be obtained.
- the bundle of reinforcing fibers obtained by arranging a plurality of reinforcing fibers in one direction is preferably a bundle of 1000 or more single fibers of reinforcing fibers, more preferably 10,000 or more.
- the upper limit of the number of reinforcing fibers is not particularly limited, but is about 500,000 in the case where the bundle of reinforcing fibers is not opened. In addition, when a bundle of reinforcing fibers is opened and used, the number of fibers may be further increased.
- a bundle of reinforcing fibers for example, a product of 6,000 (6K) bundled carbon fibers supplied from a carbon fiber manufacturer, 12,000 (12K) bundled product, 24000 (24K) bundled
- 6K 6K
- 24K 24000
- 40000 (40K) bundled products, 50000 (50K) bundled products, 60000 (60K) bundled products, and the like can be used.
- carbon fiber bundles of Torayca (registered trademark) yarn (T700SC-24000, etc.) manufactured by Toray Industries, Inc.
- Toho Tenax A bundle of carbon fibers from Tenax (registered trademark), or a bundle of a plurality of these can also be used.
- these carbon fiber bundles can be used as they are without being subjected to a fiber-opening treatment or the like, and are excellent in productivity. It may be a bundle of carbon fibers subjected to the fiber opening treatment.
- the bundle of carbon fibers may be a non-twisted yarn, a twisted yarn, or a flame-retardant yarn.
- the bundle of reinforcing fibers in the present embodiment has a strip shape.
- the length in the fiber axis direction is 5 mm or more and 500 mm or less
- the length (width) in the direction perpendicular to the fiber axis direction is about 1 mm to 300 mm
- the fiber axis The length in the direction is a strip shape longer than the length in the width direction. If the length of the bundle of carbon fibers is less than 5 mm, sufficient strength may not be obtained. On the other hand, if the length exceeds 500 mm, strength variation and strength anisotropy may occur.
- the length of the bundle of reinforcing fibers in the fiber axis direction is more preferably 10 mm to 100 mm.
- the width of the bundle of reinforcing fibers is more preferably 3 mm to 30 mm.
- the length of the reinforcing fibers constituting the bundle of strip-shaped reinforcing fibers is preferably 5 mm to 500 mm. That is, the length of each reinforcing fiber constituting the bundle of strip-like reinforcing fibers is substantially the same as the length of the bundle of strip-like reinforcing fibers obtained by bundling a plurality of these reinforcing fibers in one direction. Good.
- the thickness of the strip-shaped reinforcing fiber bundle is not particularly limited, but it is preferable that the strip-shaped reinforcing fiber bundle is shorter than the length and width in the fiber axis direction of the strip-shaped reinforcing fiber bundle.
- the approximate thickness of the bundle of strip-like reinforcing fibers is about 0.02 mm to 10 mm, and is preferably 0.2 mm to 5 mm from the viewpoint of the strength of the obtained molded body.
- the second layer 20 is made of a fiber reinforced resin material including a thermoplastic resin and a long fiber reinforced fiber.
- the second layer 20 is laminated on at least one side of the first layer 10. That is, the first layer 10 is laminated on one side of the second layer 20. From the viewpoint of strength and appearance quality, the second layer 20 may be laminated on both surfaces of the first layer 10 as shown in FIG. 1B.
- the same fibers as those of the first layer 10 can be used.
- carbon fiber is particularly preferable.
- the reinforcing fiber constituting the first layer 10 As described above, a bundle of strip-like reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction is used, but the second layer 20 is constituted.
- the reinforcing fibers to be used long-fiber reinforcing fibers are used.
- the reinforcing fibers constituting the second layer 20 are preferably woven fabrics containing long-fiber reinforcing fibers.
- woven fabrics containing such reinforcing fibers include plain woven fabrics obtained by using long fiber bundles of carbon fibers such as 6K, 12K, 24K, 40K, 50K, 60K, or bundles thereof. Examples include twill fabrics and satin fabrics. In addition, these carbon fiber long fiber bundles may be opened or not opened.
- thermoplastic resin constituting the second layer 20 the same thermoplastic resin as that constituting the first layer 10 can be used, preferably a thermoplastic epoxy resin, more preferably post-reaction.
- the mold is a thermoplastic epoxy resin.
- the thickness of the outer layer of the second layer 20 is not particularly limited, but is about 0.02 mm to 10 mm.
- the molded body 1 in the present embodiment is obtained by processing and molding a fiber reinforced resin material including a thermoplastic resin and a bundle of strip-shaped reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction. It is made of a fiber reinforced resin material including a first layer 10 in which a bundle of strip-like reinforcing fibers is randomly laminated in three dimensions, and a thermoplastic resin and a reinforcing fiber of a long fiber, and at least the first layer 20 And a second layer 20 formed on one side.
- the shape of the molded body 1 in the present embodiment is a flat sheet shape, but is not particularly limited, and may be uneven, such as a housing of a television or the like. Moreover, the flat sheet-like molded object 1 may be manufactured and processed into the target shape at an arbitrary time.
- the thermoplastic resin since the thermoplastic resin is used for both the first layer 10 and the second layer 20, it can be easily heated and pressurized at an arbitrary time. A molded body having an arbitrary shape can be obtained. Further, by using a post-reaction type thermoplastic resin, a molded body having more stable performance in both strength and moldability can be obtained.
- corrugation formed in a molded object may be less than 1 cm, 1 cm or more, Furthermore, 3 cm or more, Furthermore, May be 5 cm or more.
- the molded body 1 uses a fiber-reinforced resin material including a thermoplastic resin and a bundle of strip-shaped reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction.
- the bundle of strip-shaped reinforcing fibers has the first layer 10 that is randomly stacked three-dimensionally, anisotropy is suppressed. That is, the reinforcing fibers are arranged in one direction as a bundle of reinforcing fibers, but a plurality of reinforcing fiber bundles constituting the first layer 10 are randomly arranged in three dimensions.
- the molded body 1 in the present embodiment does not have anisotropy that occurs in a fiber-reinforced resin molded body obtained by arranging the opened fibers of carbon fibers in one direction, and in any direction. Uniform strength. Moreover, the molded body 1 according to the present embodiment has a delamination that occurs in a fiber-reinforced resin molded body in which a plurality of spread fabrics are laminated even when vibration or impact is applied to the final product during pressure molding. This phenomenon can also be suppressed.
- the molded product is easily cracked when a large force is applied, and the fracture surface of the cracked portion is sharp, and the cut surface is Easy to be exposed. For this reason, in the unlikely event that this fiber-reinforced resin molded body is cracked, there is a risk of causing secondary damage such as generating cuts in the body due to the fracture surface.
- the molded body 1 according to the present embodiment since a plurality of bundles of reinforcing fibers constituting the first layer 10 are randomly laminated in a three-dimensional manner, a large force is applied to cause cracking. Even if it exists, while being able to suppress that a fracture surface becomes sharp, it can suppress that the sharp fracture surface is exposed. Thereby, since generation
- the molded body 1 in the present embodiment is excellent in toughness and impact resistance, it is difficult to crack when a large force is applied, and even if it is cracked, the strength is greatly reduced at a time. Without falling in several stages. Thereby, when a molded object cracks, it can suppress that a big damage generate
- the length of the reinforcing fiber used for the first layer 10 of the molded body 1 in the present embodiment is 10 mm or more and 30 mm or less, it will not break unless it has a certain force or more. It is difficult to form a cross section.
- the length of the fiber reinforced resin material and the reinforced fiber is more than 30 mm, and more preferably more than 40 mm, it is difficult to crack even when subjected to a stronger impact, and even if it is cracked, it is difficult to form a sharp fracture surface.
- the characteristic of the fiber reinforced resin molding obtained can be adjusted by changing the length of a fiber reinforced resin material and a reinforced fiber.
- the molded object 1 in this Embodiment has the 1st layer 10 and the 2nd layer 20, especially as shown to FIG.
- the first layer 10 is a molded body having a thickness of 2 mm or less and an unevenness depth of more than 1 cm, Molding obtained by heating and pressing even when the length of the bundle of reinforcing fibers used in the first layer 10 or the length of the reinforcing fibers is shorter than the depth of the irregularities. A reduction in appearance quality such as a hole in the body can be suppressed, and a large variation in strength can be suppressed.
- the fiber volume content (Vf value) of the molded body 1 in the present embodiment is preferably 30% to 80%.
- the Vf value of the molded body 1 is preferably 40% or more, and more preferably 50% or more.
- the Vf value of the molded body 1 is preferably 70% or less, and more preferably 60% or less.
- the Vf% value of the molded body 1 is preferably 50% or less, and more preferably 45% or less so that no space is generated. Further, by removing the air in the first layer 10, the second layer 20 and between the layers by performing pressurization in a vacuum environment or increasing the heating temperature to lower the viscosity of the resin. It is possible to suppress the generation of a space in the molded body 1. If there is a space in the molded body 1, the strength of the molded body 1 may decrease or the strength may vary.
- the Vf value of the molded body 1 is small, the strength of the molded body 1 may be reduced. For this reason, when the high intensity
- the thickness of the molded body 1 in the present embodiment is not particularly limited, and can be arbitrarily set for the intended use of the molded body.
- the thickness of the molded body 1 is, for example, 0.07 mm or more, more preferably 0.1 mm or more, more preferably 0.2 mm or more and 200 mm or less, and further preferably 1 mm or more and 70 mm or less from the viewpoint of strength and moldability.
- the molded body 1 in the present embodiment has other resin sheets that are colored on at least one of the surfaces serving as the outer layers of the first layer 10 and the second layer 20 in order to enhance designability and visibility.
- a retroreflective sheet, a phosphorescent sheet, or the like may be laminated.
- the molded body 1 in the present embodiment can be molded even after the resin is cured, compared to a molded body composed of only a thermosetting resin, and is molded like a thermosetting epoxy resin. It is easy to use without the need for low-temperature storage and storage period problems, and does not require a long curing time, which is excellent from the viewpoint of productivity.
- the molded object 1 in this Embodiment is compared with the molded object obtained using the sheet-like thing obtained using a strong fiber fabric and a thermoplastic resin, and the bundle of a strip-like strong fiber, and a thermoplastic resin.
- strong fibers and resin such as automotive parts such as automobile chassis, building materials such as reinforcing bars, columns, and beams, or TVs, PCs, refrigerators, etc. It can be used for various purposes such as housings for electrical appliances.
- carbon fiber is used as the reinforcing fiber
- epoxy resin is used as the thermoplastic resin.
- the manufacturing method of the molded body 1 in the present embodiment includes a step of producing a sheet-like material made of a fiber reinforced resin material including a thermoplastic resin and a long fiber reinforced fiber, and a thermoplastic resin and a plurality of reinforced fibers.
- the fiber reinforced resin material including the thermoplastic resin and the long fiber reinforced fibers is for forming the second layer 20 and is formed as a sheet-like material.
- a strip-shaped fiber-reinforced resin material including a thermoplastic resin and a bundle of reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction is for forming the first layer 10 and is a laminate. Formed as.
- these sheet-like materials and laminates can be formed by a known method, a preferable method will be described below.
- the reinforcing fiber and thermoplastic resin used for producing the sheet-like material and the laminate can apply the materials used for the first layer 10 and the second layer 20 described above.
- a thermoplastic resin solution By applying a thermoplastic resin solution to a woven fabric of reinforcing fibers, a strip including a thermoplastic resin and a fiber-reinforced resin material including long-fiber reinforcing fibers and a thermoplastic resin and a plurality of reinforcing fibers arranged in one direction.
- a fiber-reinforced resin material can be obtained.
- the reinforcing fibers including the long fibers in the fiber reinforced resin material including the thermoplastic resin used for the second layer 20 and the reinforcing fibers of the long fibers may be in a woven shape.
- the reinforcing fibers including the long fibers used when producing the sheet-like material may be in a woven shape. If the reinforcing fibers containing long fibers are woven, the shape of the reinforcing fibers containing long fibers will be stable even when heated. Can effectively suppress the formation of holes in the molded body, and the molded body obtained has an aesthetic appearance.
- thermoplastic resin solution a solution obtained by heating and dissolving a thermoplastic resin can be used, but a post-reaction type thermoplastic resin, a solvent and a curing agent for dissolving and dispersing the post-reaction type thermoplastic resin. It is good to contain at least.
- thermoplastic resin solution is not limited to a solution in which a solute is completely dissolved in a solvent, but may be an emulsion or a dispersion.
- Solvents for thermoplastic resin solutions include water, dimethylformamide, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methanol, ethanol, butanol, isopropyl alcohol , Methyl cellosolve, cellosolve, or anone.
- Examples of the curing agent for the thermoplastic resin solution include a crosslinking agent, a catalyst, a polymerization initiator, and a polymerization accelerator.
- examples include amine compounds such as tertiary amines, acid anhydride compounds, mercaptan compounds, phenol resins, amino resins, dicyandiamide, and Lewis acid complex compounds.
- a block type crosslinking agent having a functional group number of more than 2 or a functional group number of 2 or more, for example, a block type isocyanate crosslinking agent may be used.
- thermoplastic resin solution may contain additives such as antioxidants, ultraviolet absorbers, pigments, thickeners, emulsifiers, or dispersants without departing from the object of the present invention.
- the viscosity of the thermoplastic resin solution is preferably 5 mPa ⁇ s or more and 1000 mPa ⁇ s or less.
- the viscosity of the thermoplastic resin solution is further preferably 10 mPa ⁇ s or more, and more preferably 50 mPa ⁇ s or more.
- the viscosity of the thermoplastic resin solution is 1000 mP ⁇ s or less, the thermoplastic resin can penetrate into the bundle of reinforcing fibers.
- the viscosity of the thermoplastic resin solution is preferably 800 mPa ⁇ s or less, and more preferably 500 mPa ⁇ s or less.
- thermoplastic resin solution As a method for applying a thermoplastic resin to a bundle of reinforcing fibers or a woven fabric, a dipping method in which the bundle of reinforcing fibers or the woven fabric is immersed in a thermoplastic resin solution, or after a bundle of reinforcing fibers or a fabric is immersed in a thermoplastic resin solution, mangle Dip nip method to squeeze, etc., transfer method in which a thermoplastic resin solution is attached to a kiss roll or gravure roll, and the thermoplastic resin is transferred from the kiss roll to a bundle of reinforcing fibers or fabric, or a mist-like thermoplastic resin solution And a spray method for imparting to a bundle of reinforcing fibers or a woven fabric.
- the thermoplastic fiber solution can be reinforced with a bundle of reinforcing fibers or fabrics attached with a thermoplastic resin solution through dies or rolls or in contact with rolls.
- the amount of the thermoplastic resin applied to the bundle of reinforcing fibers or the fabric can be adjusted by pushing in the resin or removing the excess thermoplastic resin.
- the amount of the thermoplastic resin to be applied to the bundle of reinforcing fibers and the woven fabric is determined by the above method so that the Vf value of the molded body becomes a preferable value.
- the amount of the thermoplastic resin in the plastic resin solution may be adjusted.
- thermoplastic resin solution since the viscosity of the thermoplastic resin solution can be lowered, even when the thermoplastic resin is applied to a bundle of reinforcing fibers or one side of a woven fabric by a transfer method, the transfer surface of the transferred thermoplastic resin
- the thermoplastic resin can be easily infiltrated into the bundle of the reinforced carbon fibers by bringing them into contact with a roll.
- thermoplastic resin After the thermoplastic resin is applied to the bundle of reinforcing fibers and the woven fabric, drying and / or heat treatment is performed. In addition, you may perform drying and heat processing simultaneously. At the stage of obtaining the fiber reinforced resin material, the thermoplastic resin may be completely reacted, but the reaction is stopped to some extent (or the reaction rate is reduced), and the molded product is produced. The thermoplastic resin may be completely reacted.
- At least one of the purposes of drying or heat treatment after applying a thermoplastic resin to a bundle of reinforcing fibers or woven fabric is to eliminate the surface tack of the fiber reinforced resin material.
- the fiber reinforced resin material By eliminating the tack on the surface of the fiber reinforced resin material, handling in the manufacturing process of the molded body is improved, and productivity can be improved.
- the fiber reinforced resin material by using the fiber reinforced resin material, the first layer 10 and the molded body 1 having no anisotropy can be easily obtained, and handling is good in the manufacturing process and productivity can be improved. it can.
- the temperature and time of drying and heat treatment after applying the thermoplastic resin to the bundle of reinforcing fibers and the woven fabric depend on the types of the thermoplastic resin, the curing agent and the solvent, but in the case of an epoxy resin, the drying is 40 to 100 ° C.
- the heat treatment is preferably performed at 100 ° C. to 250 ° C. for 1 minute to 1 hour. More preferably, drying is at 50 to 80 ° C. for 10 to 30 minutes, and heat treatment is at 120 to 180 ° C. for 3 to 40 minutes. If it is said range, the fiber reinforced resin molding excellent in the external appearance quality can be manufactured with the outstanding productivity.
- thermoplastic resin is added to the above-mentioned bundle of carbon fibers, dried and / or
- the carbon fiber provided with the thermoplastic resin may be cut into a strip shape by cutting in a direction substantially perpendicular to the fiber axis direction of a bundle of reinforcing fibers composed of a plurality of reinforcing fibers arranged in one direction.
- the preferred length of the strip-like fiber reinforced resin material is as described in the bundle of reinforcing fibers.
- a fiber-reinforced resin material containing a thermoplastic resin and long-fiber reinforcing fibers, and a strip-like fiber containing a bundle of reinforcing fibers in which a thermoplastic resin and a plurality of reinforcing fibers are arranged in one direction.
- a reinforced resin material is obtained.
- a sheet-like product made of a fiber-reinforced resin material containing a thermoplastic resin and long-fiber reinforcing fibers, and a reinforcing material obtained by arranging the thermoplastic resin and a plurality of reinforcing fibers in one direction.
- a layered product can be obtained by laminating a laminate in which strip-like fiber reinforced resin materials including a bundle of fibers are randomly laminated in three dimensions.
- strip-like fiber reinforced fibers are separately laminated on a stainless steel plate or the like in a three-dimensional random manner, and if necessary, lightly pressed in the same manner as described above or heated while pressing and partially
- the laminate is produced by laminating the laminate on a sheet-like article made of a fiber reinforced resin material containing one or more thermoplastic resins and long fiber reinforced fibers. May be obtained.
- a layered material may be obtained by arranging a sheet-like material made of a fiber-reinforced resin material containing a thermoplastic resin and long fibers of reinforcing fibers.
- the layered product of the sheet-like product and the laminate is heated and pressurized. Thereby, the molded object 1 can be manufactured.
- a molded product may be obtained by performing heating and pressurization simultaneously, the layered product is heated to sufficiently soften the thermoplastic resin, and then pressurization or heating until the thermoplastic resin is cured. You may obtain a molded object by pressurizing, pressing.
- Examples of the pressurizing method include a mold pressing method, an autoclave method, and a heating / cold pressing method.
- the heating temperature is about 150 to 400 ° C., although it depends on the type of thermoplastic resin used, the glass transition point of the reinforcing fiber, the layered product, or the thickness of the obtained molded product.
- the heating temperature is preferably 300 ° C. or lower.
- the pressure during pressurization is about 1 to 50 MPa.
- the pressurization time is about 1 to 60 minutes.
- the above layered material is passed between the heating and pressing rollers after passing through a pressing roller or after heating or without prior heating. May be allowed to pass.
- pressurization is preferably performed in a vacuum environment. Thereby, it can suppress that a space generate
- the object is then heated and pressurized using a mold or the like as described above according to the intended shape and application, and then cooled. What is necessary is just to shape
- pressurization is performed in a vacuum environment, or heating and pressurization are performed simultaneously. Of course, you may heat a molded object previously.
- the heating and pressurizing conditions are preferably lower temperature and lower pressure than when manufacturing a molded body having irregularities.
- thermoplastic resin solution when the cross-linking agent added to the thermoplastic resin solution is heated at a temperature lower than the temperature at which the cross-linking reaction starts, a flat sheet is once produced to produce a molded article having a desired shape.
- a molded body When heated at a temperature equal to or higher than the temperature at which the cross-linking reaction is started, a molded body that can be easily molded and has excellent shape thermal stability can be easily obtained.
- a molded body is obtained by the manufacturing method as described above, a molded body having large irregularities that has been difficult to be molded can be obtained. Therefore, various molded articles can be obtained using a fiber reinforced resin material using reinforced fibers, particularly carbon fibers.
- molded body according to the present embodiment will be further described by examples, but the present invention is not limited to these examples.
- a molded body having the structure shown in FIG. 1B was produced.
- “part” means “part by mass”.
- Example 1 ⁇ Production of laminate>
- a bundle of 24,000 single fibers of carbon fibers (24K) was used as a bundle of reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction (PAN-based carbon fiber (manufactured by Toray Industries, Inc.). T700SC)).
- thermoplastic resin solution was applied using a kiss roll on one side of the carbon fiber bundle while drawing the carbon fiber bundle as it was from the drum around which the carbon fiber bundle was wound without performing the fiber opening treatment.
- Thermoplastic resin solution > -Thermoplastic epoxy resin (post-reactive resin. DENATEITE XNR6850V, manufactured by Nagase ChemteX Corporation) 100 parts-Curing agent (DENATEITE XNH6850V, manufactured by Nagase ChemteX Corporation) 6.5 parts-Methyl ethyl ketone 10 parts
- the viscosity of the thermoplastic resin solution was 80 mPa ⁇ s. This viscosity was measured using a B-type viscometer (Toki Sangyo Co., Ltd .: TVB-15 type viscometer). Measured at 20, 12 rpm and room temperature (15 ° C.).
- the upper and lower surfaces of the bundle of carbon fibers provided with the thermoplastic resin solution are in contact with four rolls (the upper surface of the bundle of carbon fibers is contacted twice and the lower surface is contacted twice: the upper surface and the lower surface are alternately contacted twice each. ) And then dried at 60 ° C. for 20 minutes, followed by heat treatment at 150 ° C. for 20 minutes to react with the thermoplastic resin, then cooled at room temperature, wound on a drum, 50 m in length
- a tape-like fiber-reinforced resin material obtained by adding a post-reaction type thermoplastic resin to a bundle of reinforcing fibers having a width of 4 mm and a thickness of 0.38 mm was obtained.
- the glass transition point of the thermoplastic resin in the thermoplastic resin solution was 100 ° C.
- the tape-like fiber reinforced resin material is cut so as to have a length of 20 to 30 mm substantially perpendicular to the fiber axis direction of the carbon fiber, and is a strip having a length of 20 to 30 mm, a width of 4 mm, and a thickness of 0.38 mm.
- a fiber-reinforced resin material (a bundle of strip-shaped reinforcing fibers) was obtained.
- the Vf value of the obtained fiber reinforced resin material was 45%.
- the length of the carbon fiber in the obtained fiber reinforced resin material is the same as the length of the fiber reinforced resin material because the carbon fiber is a long fiber, and is 20 to 30 mm.
- thermoplastic resin had entered the center of the bundle of carbon fibers.
- strip-shaped fiber reinforced resin materials were randomly laminated three-dimensionally in a stainless steel mold, heated at 170 ° C. for 5 minutes, cooled, and taken out from the stainless steel mold. As a result, a laminate in which a part of the thermoplastic resin melted and a part of each strip-like fiber reinforced resin material adhered was obtained.
- a plain fabric obtained by using carbon fibers of long fibers as reinforcing fibers of long fibers (Torayca (registered trademark) CO6343B manufactured by Toray Industries, Inc. 3K carbon fiber bundle obtained by bundling 3000 carbon fibers
- this plain woven fabric was immersed in the same thermoplastic resin solution as that used when the laminate was produced, and the thermoplastic resin solution was applied to the plain woven fabric.
- the upper and lower surfaces of the plain fabric to which the thermoplastic resin solution is applied are brought into contact with 10 rolls (the upper surface of the plain fabric is contacted 5 times and the lower surface is contacted 5 times: the upper surface and the lower surface are alternately contacted 5 times each).
- the upper surface of the plain fabric is contacted 5 times and the lower surface is contacted 5 times: the upper surface and the lower surface are alternately contacted 5 times each).
- a sheet-like fiber reinforced resin material provided with a mold type thermoplastic resin was obtained.
- the thermoplastic resin in the thermoplastic resin solution had a glass transition point of 100 ° C. and a Vf value of 50%.
- FIG. 3 is a view showing the flat molded body obtained in this manner.
- the molded body was preheated at 200 ° C., and subsequently heated using a mold at 200 ° C., 500 kN, 3 minutes, and a depth of unevenness of 5 cm. By applying pressure, a molded product having an unevenness depth of 5 cm was obtained.
- the thickness of the obtained molded body was 1.86 mm.
- the thickness of the first layer 10 was 1.3 mm, and the thickness of each of the second layers 20 was 0.28 mm. Further, the Vf value of the molded body was 52%.
- FIGS. 4 and 5 are views showing the molded body thus obtained, FIG. 4 is an external view when viewed from the front surface, and FIG. 5 is an external view when viewed from the back surface.
- the molded body obtained in this way had no large holes or the like, appeared a texture of the woven fabric, and was excellent in design.
- the obtained molded body was cut and the cross section was observed with an electron microscope, it was filled with carbon fiber and a thermoplastic resin, and no space (cavity) was found inside the molded body.
- Example 2 ⁇ Preparation of laminated layered product>
- a bundle of 24,000 single fibers of carbon fibers (24K) was used as a bundle of reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction (PAN-based carbon fiber (manufactured by Toray Industries, Inc.). T700SC)).
- thermoplastic resin solution was applied using a kiss roll on one side of the carbon fiber bundle while drawing the carbon fiber bundle as it was from the drum around which the carbon fiber bundle was wound without performing the fiber opening treatment.
- Thermoplastic resin solution > -Thermoplastic epoxy resin (post-reactive resin. DENATEITE XNR6850V, manufactured by Nagase ChemteX Corporation) 100 parts-Curing agent (DENATEITE XNH6850V, manufactured by Nagase ChemteX Corporation) 6.5 parts-Curing agent (trifunctional) Book type isocyanate compound) 5 parts ⁇ Methyl ethyl ketone 10 parts
- the viscosity of the thermoplastic resin solution was 80 mPa ⁇ s. This viscosity was measured using a B-type viscometer (Toki Sangyo Co., Ltd .: TVB-15 type viscometer). Measured at 20, 12 rpm and room temperature (15 ° C.).
- thermoplastic resin solution After the upper and lower surfaces of the bundle of carbon fibers to which the thermoplastic resin solution has been applied are brought into contact with four rolls (the upper and lower surfaces of the bundle of carbon fibers are alternately contacted twice, respectively), 60 Drying at 20 ° C. for 20 minutes, followed by heat treatment at 150 ° C. for 20 minutes, followed by cooling at room temperature, winding on a drum, post-reaction type heat into a bundle of reinforcing fibers having a width of 4 mm and a thickness of 0.38 mm A tape-like fiber reinforced resin material provided with a plastic resin was obtained. The glass transition point of the thermoplastic resin in the thermoplastic resin solution was 100 ° C.
- the tape-like fiber reinforced resin material is cut so as to have a length of 30 mm substantially perpendicular to the fiber axis direction of the carbon fiber, and a strip-like fiber reinforced fiber having a length of 30 mm, a width of 4 mm, and a thickness of 0.38 mm.
- a resin material (a bundle of strip-shaped reinforcing fibers) was obtained.
- the Vf value of the obtained fiber reinforced resin material was 45%.
- the length of the carbon fiber in the obtained fiber reinforced resin material is the same as the length of the fiber reinforced resin material, and is 30 mm.
- thermoplastic resin had entered the center of the bundle of carbon fibers.
- strip-like fiber reinforced resin materials were randomly laminated three-dimensionally in a stainless steel mold, heated at 270 ° C. for 5 minutes, cooled, and taken out from the stainless steel mold. As a result, a laminate in which a part of the thermoplastic resin melted and a part of each strip-like fiber reinforced resin material adhered was obtained.
- a plain fabric obtained by using carbon fibers of long fibers as reinforcing fibers of long fibers (Torayca (registered trademark) CO6343B manufactured by Toray Industries, Inc. 3K carbon fiber bundle obtained by bundling 3000 carbon fibers
- this plain woven fabric was immersed in the same thermoplastic resin solution as that used when the laminate was produced, and the thermoplastic resin solution was applied to the plain woven fabric.
- thermoplastic resin in the thermoplastic resin solution had a glass transition point of 100 ° C. and a Vf value of 50%.
- the layered material was preheated at 270 ° C., and subsequently heated at 270 ° C., 4 MPa for 15 minutes using a mold having an uneven depth of 5 cm. By applying pressure, a molded product having an unevenness depth of 5 cm was obtained.
- the thickness of the obtained molded body was 3.66 mm.
- the thickness of the first layer 10 obtained from the laminate was 3.10 mm, and the thickness of the second layer 20 obtained from the sheet-like material was 0.28 mm. Further, the Vf value of the molded body was 52%.
- the obtained molded body had no large holes and the like, and the appearance of the fabric structure appeared, and the design was excellent.
- the obtained molded body was cut and the cross section was observed with an electron microscope, it was filled with carbon fiber and a thermoplastic resin, and no space (cavity) was found inside the molded body.
- the layered product obtained by sandwiching one laminate between the two sheet-shaped materials is not the 270 °, but the above-mentioned molded body is 200 in a vacuum environment state ( ⁇ 0.1 MPa).
- a vacuum environment state ⁇ 0.1 MPa
- the shape was slightly deformed but could not be formed into the desired shape, and Many voids were observed in the laminate. Therefore, although a molded body could be obtained at 270 ° C., the intended molded body could not be obtained at 200 ° C., and the shape was improved in thermal stability when a crosslinking agent was added to the thermoplastic resin solution. It was confirmed that
- Reference Example 1 the layered material of Example 1 was preheated at 200 ° C. in a vacuum environment ( ⁇ 0.1 MPa), and subsequently, 200 ° C., 500 kN, 10 minutes, and the depth of unevenness was 0.5 cm. By pressing with a mold using a mold, a molded body having a concavo-convex depth of 0.5 cm was obtained. The obtained molded body had a thickness of 1.50 mm and a Vf value of 48%.
- FIG. 6 is a view showing a state when the molded body thus obtained is viewed from the surface. As shown in FIG. 6, the molded body thus obtained had no large holes or the like.
- Reference Example 2 In Reference Example 2, the layered material of Example 1 was preheated at 200 ° C. in a vacuum environment state ( ⁇ 0.1 MPa), and then a mold having a depth of unevenness of 5 cm at 200 ° C., 500 kN for 3 minutes. By applying pressure while heating using a, a molded body having a depth of 5 cm was obtained. The obtained molded body had a thickness of 1.50 mm and a Vf value of 52%.
- FIGS. 7 and 8 are views showing the molded body thus obtained, FIG. 7 is an external view when viewed from the front surface, and FIG. 8 is an external view when viewed from the back surface. As shown in FIGS. 7 and 8, large holes were formed on the bottom and side surfaces of the molded body of Reference Example 2.
- the molded body in this example has excellent appearance quality and excellent strength, and even a molded article (molded article) with deep irregularities can be easily produced without opening a hole. It can be used as various parts and products that have been difficult to use due to the problem of formability. Therefore, it is possible to provide a product that can be reduced in weight, increased in strength, and can save energy associated with weight reduction.
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Abstract
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US15/329,766 US20170232702A1 (en) | 2014-07-31 | 2015-07-09 | Molded object and method of manufacturing same |
EP15827466.2A EP3175979B1 (fr) | 2014-07-31 | 2015-07-09 | Objet moulé et procédé de production associé |
JP2016537731A JP6715769B2 (ja) | 2014-07-31 | 2015-07-09 | 成形体及びその製造方法 |
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PCT/JP2015/003471 WO2016017080A1 (fr) | 2014-07-31 | 2015-07-09 | Objet moulé et procédé de production associé |
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US (1) | US20170232702A1 (fr) |
EP (1) | EP3175979B1 (fr) |
JP (1) | JP6715769B2 (fr) |
WO (1) | WO2016017080A1 (fr) |
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JP2018030986A (ja) * | 2016-08-26 | 2018-03-01 | 株式会社クラレ | プリプレグ、成形体、成形体の製造方法、プリプレグの製造方法、積層成形体の製造方法及び二次加工成形体の製造方法 |
JP2018144465A (ja) * | 2017-03-02 | 2018-09-20 | 小松精練株式会社 | 木製材料 |
JP2019044542A (ja) * | 2017-09-06 | 2019-03-22 | 小松マテーレ株式会社 | コンクリート柱補強器具 |
JP2019070288A (ja) * | 2017-10-11 | 2019-05-09 | 株式会社竹中工務店 | 建築資材、及びコンクリート打設用の型枠 |
JPWO2018142962A1 (ja) * | 2017-02-02 | 2019-11-21 | 東レ株式会社 | 繊維強化プラスチックの製造方法 |
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JP2020199643A (ja) * | 2019-06-06 | 2020-12-17 | 双葉電子工業株式会社 | 炭素繊維強化プラスチック板および炭素繊維強化プラスチック板の製造方法 |
JP6806292B1 (ja) * | 2019-07-30 | 2021-01-06 | 三菱瓦斯化学株式会社 | 成形品の製造方法および複合材料 |
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JP7011888B2 (ja) | 2016-08-26 | 2022-01-27 | 株式会社クラレ | プリプレグ、成形体、成形体の製造方法、プリプレグの製造方法、積層成形体の製造方法及び二次加工成形体の製造方法 |
JP2018062638A (ja) * | 2016-10-07 | 2018-04-19 | サンコロナ小田株式会社 | 一方向プリプレグおよび繊維強化熱可塑性樹脂シート |
JP6176691B1 (ja) * | 2016-10-07 | 2017-08-09 | サンコロナ小田株式会社 | 一方向プリプレグおよび繊維強化熱可塑性樹脂シート |
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JPWO2018142962A1 (ja) * | 2017-02-02 | 2019-11-21 | 東レ株式会社 | 繊維強化プラスチックの製造方法 |
JP2018144465A (ja) * | 2017-03-02 | 2018-09-20 | 小松精練株式会社 | 木製材料 |
JP2019044542A (ja) * | 2017-09-06 | 2019-03-22 | 小松マテーレ株式会社 | コンクリート柱補強器具 |
JP7049800B2 (ja) | 2017-10-11 | 2022-04-07 | 株式会社竹中工務店 | 建築資材、及びコンクリート打設用の型枠 |
JP2019070288A (ja) * | 2017-10-11 | 2019-05-09 | 株式会社竹中工務店 | 建築資材、及びコンクリート打設用の型枠 |
JPWO2020009125A1 (ja) * | 2018-07-03 | 2021-08-02 | フクビ化学工業株式会社 | Cfrpシート、cfrpシートを用いた積層体、及びcfrpシートの製造方法 |
WO2020009125A1 (fr) * | 2018-07-03 | 2020-01-09 | フクビ化学工業株式会社 | Feuille de cfrp, corps stratifié utilisant une feuille de cfrp et procédé de production de feuille de cfrp |
JP7118149B2 (ja) | 2018-07-03 | 2022-08-15 | フクビ化学工業株式会社 | Cfrpシート、cfrpシートを用いた積層体、及びcfrpシートの製造方法 |
US11603442B2 (en) | 2018-12-04 | 2023-03-14 | Suncorona Oda Co., Ltd. | Fiber-reinforced thermoplastic resin sheet, molded body of fiber-reinforced thermoplastic resin sheet, and manufacturing method of fiber-reinforced thermoplastic resin sheet |
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JP7005557B2 (ja) | 2019-06-06 | 2022-01-21 | 双葉電子工業株式会社 | 炭素繊維強化プラスチック板および炭素繊維強化プラスチック板の製造方法 |
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US11932741B2 (en) | 2019-07-30 | 2024-03-19 | Mitsubishi Gas Chemical Company, Inc. | Method for manufacturing molded article, and composite material |
WO2024111127A1 (fr) * | 2022-11-25 | 2024-05-30 | 日産自動車株式会社 | Matériau de résine renforcé par des fibres pour carrosserie de voiture |
Also Published As
Publication number | Publication date |
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EP3175979B1 (fr) | 2020-03-04 |
EP3175979A1 (fr) | 2017-06-07 |
JP6715769B2 (ja) | 2020-07-01 |
JPWO2016017080A1 (ja) | 2017-05-18 |
US20170232702A1 (en) | 2017-08-17 |
EP3175979A4 (fr) | 2018-03-28 |
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